Reaction products of n-acylated polyalkylene-polyamines with alkenyl succinic acid anhydrides



Patented Sept. 25, 1951 NHTED STATES 2,568,876 GFFICE REACTION PRODUCTSF N-ACYLATED POLYALKYLENE-POLYAMINES WITH ALKENYL SUCCINIC ACID ANHY-DRIDES No Drawing. Application November 14, 1949, Serial No. 127,278

23 Claims. i

This invention relates, broadly, to organic nitrogen compounds and tocorrosion-inhibiting compositions containing the same. It is morespecifically concerned with the reaction products obtained by reactingmonocarboxylic acids, polyalkylenepolyamines having one more nitrogenatom per molecule than there are alkylene groups in the molecule, andalkenyl succinic acid anhydrides; and with corrosion-inhibitingcompositions comprising suitable vehicles containing these reactionproducts.

As is well known to those familiar with the art, whenever machines anddevices have been constructed in whole or in part of metals,particularly ferrous metals, the occurrence of surface corrosion haspresented serious problems. For example, farming implements arefrequently stored under conditions where they are subject to rusting.Rusting also presents problems in the storage of infrequently usedmachinery, in the shipment of machined metal parts, such as sewingmachine parts and gun barrels, and in the use of structural steelmembers, such as bridge trusses. These difi'iculties have been overcomein part by coating the exposed surfaces with paints, greases, oils andthe like. In many cases, however, it has been disadvantageous to usethese expedients since it is often necessary to remove such coatingscompletely before the object is used. Accordingly, recourse has been hadto corrosion-inhibiting compositions which can be applied to metalsurfaces and which can be removed easily and cheaply.

In the field of lubrication, the rusting of ferrous metal surfaces hasbeen a common occurrence. This has been a serious problem in steamturbines, particularly during the initial operation of newinstallations. The rusting is most pronounced at points where theclearance between bearing surfaces is very small, such as in thegovernor mechanism. This is usually caused by water entering the oilsupply, as by condensation, and becoming entrained in the oil throughoutthe circulating system, thereby coming into contact with the ferrousmetal surfaces. Manifestly, this constitutes a menace to the operationallife of the turbine.

Many materials have been proposed as coating compositions or as additionagents for lubricating oils to inhibit rusting. In United States LettersPatents Nos. 2,124,628, 2,133,734 and 2,279,688, there were disclosedalkenyl succinic acids, and halogenated and/or sulfurized derivativesthereof, as compounds useful in the prevention of corrosion. In thesepatents, the patentees stipulate that the acids must have at least 16carbon atoms, and preferably, 20 carbon atoms per molecule.

It has now been found that a. new type of corrosion inhibitor can beproduced from alkenyl succinic acid anhydrides having any number ofcarbon atoms in the alkenyl radical thereof. It has now been discoveredthat useful corrosion inhibitors can be produced by first reacting amonocarboxylic acid with a polyalkylenepolyamine to produce anintermediate product, and then reacting this intermediate product withan alkenyl succinic acid anhydride.

Accordingly, it is a broad object of this invention to provide novelcorrosion inhibitors. Another object is to provide corrosion inhibitorsproduced from alkenyl succinic acids having any number of carbon atomsin the alkenyl radical. A specific object is to provide corrosioninhibitors by reacting a monocarboxylic acid with apolyalkylenepolyamine to produce an intermediate product, and thenreacting this intermediate product with an alkenyl succinic acidanhydride. A more specific object is to provide substantially neutralvehicles containing such corrosion inhibitors. An important object is toprovide mineral lubricating oils containingminor amounts of corrosioninhibitors of the type described hereinbefore. Other objects andadvantages of the present invention will become apparent to thoseskilled in the art from the following detailed description.

Broadly stated, the present invention provides new compositions ofmatter obtained by reacting a monocarboxylic acid with apolyalkylenepolyamine having one more nitrogen atom per molecule thanthere are alkylene groups in the molecule, in a molar proportion varyingbetween about one and about (ac-1) to one, respectively, wherein :2represents the number of nitrogen atoms in the polyalkylenepolyaminemolecule, to produce an intermediate product, and reacting an alkenylsuccinic acid anhydride with the intermediate product, in a molarproportion varying between about (a:l) to one, respectively; the sum ofthe number of moles of the monocarboxylic acid and of the alkenylsuccinic acid anhydride reacted with each mole of saidpolyalkylenepolyamine being no greater than 11:. The present inventionprovides also a substantially neutral vehicle containing between about0.003 per cent and about 50 per cent by weight of these compositions ofmatter.

In general, the polyalkylenepolyamine reactants utilizable herein arethose compounds having the structural formula, H2N(RNH) =H, wherein R isan alkylene radical, or a hydrocarbon radical-substituted alkyleneradical, and z is an integer greater than one, there being no upperlimit to the number of alkylene groups in the molecule. It is preferred,however, to use the polyethylenepolyamines. because of their greatercommercial availability. These compounds have the formula:

wherein z is an integer varying between about two and about six. Innaming the polyalkylenepolyamine reactants, the nitrogen atoms areconsidered to be attached to the terminal carbon atoms of the maincarbon atom chain indicated in each compound name. For example,di-(lmethylamylene) triamine has the structural formula:

acrylic acid; nitrosobutyric acid; aminovaleric acid; aminohexanoicacid; heptanoic acid; heptanoic acid anhydride; 2-ethylhexanoic acid;a.- bromooctanoic acid; decanoic acid; dodecanoic In numbering the maincarbon atom chain, the carbon atom attached to the terminal --NH2radical is designated as the carbon atom in the 1-position. Similaralkylene groups recur throughout the molecule. Non-limiting examples ofthe polyalkylenepolyamine reactants are diethylenetriamine;triethylenetetramine; tetraethylenepentamine; di(methylethylene)triamine; hexapropyleneheptamine; tri-(ethylethylene)tetramine; penta-(l-methylpropylene) -hexamine; tetrabutylenepentamine;hexa-(l,1-dimethylethylene) -heptamine; di- (l-methylbutylene) triamine;pentaamylenehexamine; tri-(1,2,2- trimethylethylene) tetramine; dil-methylamylene) triamine; tetra (1,3 dimethylpropylene) pentamine;penta-(1,5-dimethylamylene) hexamine; di-(1-methyl-4-ethylbutylene)-triamine; penta (1,2 dimethyl-l-isopropylethylene) hexamine;tetraoctylenepentamine; tri-(1,4-diethylbutylene) tetramine;tridecylenetetramine; tetra- (1,4-dipropylbutylene)pentamine;didodecylenetriamine; tetratetradecylenepentamine; penta-(1-methyl-4-nonylbutylene) hexamine tril ,15- dimethylpentadecylene)-tetramine; trioctadecylenetetraamine; dieiccsylenetriamine; di-(1,2-dimethyl l4 nonyltetradecylene) triamine; di- (1,18dioctyleetedecylenel triamine; penta (1- methyl benzylethylene)hexamine; tetra-(1- methyl 3 benzylpropylene) pentamine; tri-(lmethyl-lh:.ny1-3 propylpropylene) tetramine; and tetra-(l-ethyl-Z-benzylethylene) pentamine.

The poiyalkyieizepalyamines can be prepared by sever-7:1 methods wellknown to the art. One well accepted method comprises reacting ammoniawith an alkyl, or substituted alkyl, dihalide. For example,tetraethylenepentamine has been prepared by reacting ammonia withethylene bromide.

Any monocarboxylic acid, or its acid anhydride or acid halide, can bereacted with the polyalkylenepolyamine reactant to produce theintermediate products used in preparing the reaction products of thepresent invention. The aromatic and the heterocyclic monocarboxylicacids, as well as the aliphatic monocarboxylic acids, are utilizable.Monocarboxylic acids containing substituent groups, such as halogenatoms, are also applicable herein. However, the preferred monocarboxylicacid reactants are the aliphatic monocarboxylic acids, i. e., thesaturated or unsaturated, branched-chain or straight-chain,monocarboxylic acids, and the acid halides and acid anhydrides thereof.Particularly preferred are the aliphatic monocarboxylic acid reactantshaving a relatively long carbon chain length, such as a carbon chainlength of between about 10 carbon atoms and about 30 carbon atoms.Nonlimiting examples of the monocarboxylic acid reactant are formicacid; acetic acid; fiuoroacetic acid; acetic anhydride; acetyl fluoride;acetyl chloride; propionic acid; propiolic acid; propionic acid;undecylenic acid; tetradecanoic acid; myristoyl bromide; hexadecanoicacid; palmitic acid; oleic acid; heptadecanoic acid; stearic acid;linoleic acid; linolenic acid; phenylstearic acid; xylylstearic acid;.a-dodecyltetradecanoic acid; arachidic acid; behenic acid; behenolicacid; erucic acid; erucic acid anhydride; cerotic acid; selacholic acid;heptacosanoic acid anhydride; montanic acid; melissic acid;ketotriacontanoic acid; hexahydrobenzoic acid; hexahydrobenzoyl bromide;furoic acid; chlorofuroic acid; thiophene carboxylic acid; picolinicacid; nicotinic acid; benzoic acid; benzoic acid anhydride; benzoyliodide; benzoyl chloride; toluic acid; xylic acid; chloroanthranilicacid; toluic acid anhydride; chlorodinitrobenzoic acid; cinnamic acid;cinnamic acid anhydride; aminocinnamic acid; salicylic acid;hydroxytoluic acid; iodosalicylic acid; naphthoyl chloride; andnaphthoic acid.

Test data tend to establish that the first molecule of themonocarboxylic acid reactant which reacts with the polyethylenepolyaminereactant condenses with both a terminal nitrogen atom and the nitrogenatom adjacent thereto, with the formation of two molecules of water, toform an imidazoline ring. The other molecules of the monocarboxylic acidreactant probably react with the remaining nitrogen atoms to formacylated derivatives. No evidence has been found for the presence ofmore than one imidazoline ring per molecule of intermediate. Thefollowing example furnishes evidence of the imidazoline structure:

EXAMPLE I the following analysis corresponding to the empirical formulaof the imidazoline compound:

Calculama Found Per cent C 68. 24 68. 08 11.85 12. 03 19. 91 19.78Molecular Weight 211 202 A sample of Z-methylimidazoline (M. P. 104.5-C.) was prepared in accordance with the method of Ladenberg, Ber., 27,2952 (1894). This was used as a reference compound.

An infrared spectrum was obtained on a highlyreflned white oildispersion of the reference compound. Another infrared spectrum wasobtained for liquid fraction 3. The similarity of the two spectraindicated the presence of the imldazoline ring in fraction 3. On thebasis of the results of chemical analyses and of infrared absorptionspectra, it is postulated that fraction 3 has the following structure:

CH2CHa In a similar manner, it can be postulated that apolypropylenepolyamine reactant will react to form a. A-tetrahydropyrimidine ring. [For example, the reaction between equimolarquantities of dipropylenetriamine and caprylic acid can produce theproduct:

On the other hand, polyalkylenepolyamine reactants having longeralkylene chain lengths probably will not form ring compounds. Thereaction products will be acylated, however.

Accordingly, in order to produce an intermediate product which has atleast one nitrogen atom free to react chemically with the alkenylsuccinic acid anhydride reactant to produce mixtures of reactionproducts representing the complete chemical interaction of thereactants, rather than physical mixtures of alkenyl succinic acidanhydride with intermediate products and/or the reaction productrepresenting the complete chemical interaction of the reactants, it isessential that no more than (:c2) moles of monocarboxylic acid reactantbe reacted with each mole of polyalkylenepolyamine reactant, a:representing the number of nitrogen atoms in the polyalkylenepolyaminemolecule. Thus, the proportion of monocarboxylic acid reactant topolyalkylenepolyamine reactant will vary between about 1:1,

respectively, and about (a:2) :1, respectively, when the reactionproducts, representing the complete chemical interaction of thereactants, of this invention are desired. It is especially preferred toproduce intermediate products having two unreacted nitrogen atoms. Toproduce such intermediate products, the maximum proportion ofmonocarboxylic acid reactant to polyalkylenepolyamine will be (:v3) :1,respectively.

When the number of moles of monocarboxylic acid reactant is only oneless than the number of nitrogen atoms in the polyalkylenepolyaminereactant, i. e., (z1) moles, the intermediate product apparently willnot have any nitrogen atoms free for further reaction with the alkenylsuccinic acid anhydride reactant. It has been discovered, however, thatsuch intermediate products can be combined with the alkenyl succinicacid anhydride reactant to produce products, probably physical mixtures,which ar nevertheless utilizable in accordance with the presentinvention. Therefore, the proportion of monocarboxylic acid reactant topolyalkylenepolyamine reactant varies, broadly, between about 1:1,respectively, and about (:r1) :1, respectively.

For example, when tetraethylenepentamine is utilized as thepolyalkylenepolyamine reactant, one, two, three, or even four moles of amonocarboxylic acid reactant can be reacted with each mole thereof, toproduce intermediat products suitable for the purposes contemplatedherein. If five moles of monocarboxylic acid reactant are used, theremay be an unreacted mole of monocarboxylic acid reactant, and such anintermediate product is not contemplated to be within the scope of thpresent invention. It must be strictly understood therefore, that theintermediat products of this invention are not pure, definite chemicalcompounds. The available facts indicate that the reaction involved ismuch more complex. Evidence. has been found for the formation of theimidazoline ring or the A -tetrahydropyrimidine ring is formed. However,the precise manner of reaction of the other moles of the monocarboxylicacid reactant is purely conjectural. This is substantiated by the factthat some residual acidityis always present in the intermediate product.In view of the foregoing, it will be understood that any designationassigned to these products, other than a definition comprising arecitation of the process of producing them, is not accuratelydescriptive of them.

The temperature at which the reaction between the monocarboxylic acidreactant and the polyalkylenepolyamine reactant is effected is not toocritical a factor. Since the reactions involved appear to be anamide-formation reaction and a condensation reaction, the generaltemperature conditions for such reactions, which are well known to thoseskilled in the art, are applicable. Nevertheless, it is usuallypreferred to operate at temperatures varying between about C. and aboutC. It must be strictly understood, however, that the reaction betweenthe monocarboxylic acid reactant and the polyalkylenepolyamine reactantcan be effected at temperatures substantially lower than 130 C. andsubstantially higher than 160 C., and that this invention is not to belimited to the preferred temperature range.

Water is formed as a by-product of the reaction between themonocarboxylic acid reactant and the polyalkylenepolyamine reactant. Inorder to facilitate the removal of this water, to effect a more completereaction in accordance with the principle of Le Chatelier, a hydrocarbonsolvent which forms an azeotropic mixture with water can be added to thereaction mixture. Heating 15 continued with the liquid reaction mixtureat the preferred reaction temperature, until the removal or water byazeotropic distillation has substantially ceased. In general, anyhydrocarbon solvent which forms an azeotropic mixture with water can beused. It is preferred, however, to use an aromatic hydrocarbon solventof the benzene series. Non-limiting examples of the preferred solventare benzene, toluene, and xylene. The amount of solvent used is avariable and noncritical factor. It is dependent on the size of thereaction vessel and the reaction temperature selected. Accordingly, asuificir-nt amount of solvent must be used to support the azeotropicdistillation, but a large excess must be avoided since the reactiontemperature will be lowered thereby. Water produced by the reaction canalso be removed by operating under reduced pressure. When operating witha reaction vessel equipped with a reflux condenser provided with a watertakeoff trap, suflicient reduced pressure can be achieved by applying aslight vacuum to the upper end of the condenser. The pressure inside thesystem is usually reduced to between about 50 and about 300 millimeters.If desired, the water can be removed also by distillation, whileoperating under relatively high temperature conditions.

The time of reaction between the -monocarboxylic acid reactant and thepolyalkylenepolyamine reactant is dependent on the weight of the charge,the reaction temperature selected, and the means employed-for rmovingthe water from the reaction mixture. Inpractice, the reaction iscontinued until the formation of water has substantially ceased. Ingeneral, the time of reaction will vary between about six hours andabout ten hours.

Any alkenyl succinic acid anhydride or the corresponding acid isutilizable for the production of the reaction products of the presentinvention. The general structural formulae of these compounds are:

Anhydride Acid wherein R is an alkenyl radical. The alkenyl radical canbe straight-chain or branched-chain; and it can be saturated at thepoint of unsaturation by the addition of a substance which adds toolefinic double bonds, such as hydrogen, suifur, bromine, chlorine, oriodine. It is obvious, of course, that there must be at least two carbonatoms in the alkenyl radical, but there is no real upper limit to thenumber of carbon atoms therein. However, it is preferred to use'analkenyl succinic acid anhydride reactant having between about 8 andabout 18 carbon atoms per alkenyl radical. In order to produce thereaction products of this invention, however, an alkenyl succinic acidanhydride or the corresponding acid must be used. Succinic acidanhydride and succinic acid are not ample, the reaction product producedby reacting an intermediate product with succinic acid anhydride is anamorphous, dark, insoluble mass. Although their use is less desirable,the alkenyl succinic acids also react, in accordance with thisinvention, to produce satisfactory reaction products. It has been found,however, that their use necessitates the removal of water formed duringthe reaction and also often causes undesirable side reactions to occurto some extent. Nevertheless, the alkenyl succinic acid anhydrides andthe alkenyl succinic acids are interchangeable for the purposes of thepresent invention. Accordingly,-when the term alkenyl succinic acidanhydride," is used herein, it must be clearly understood that itembraces the alkenyl succinic acids as well as their anhydrides, and thederivatives thereof in which the olefinic double bond has been saturatedas set forth hereinbefore. Non-limiting examples of the alkenyl succinicacid anhydride reactant are ethenyl succinic acid anhydrides; ethenylsuccinic acid; ethyl succinic acid anhydride; propenyl succinic acidanhydride; sulfurized propenyl succinic acid anhydride; butenyl succinicacid; Z-methylbutenyl succinic acid anhyutilizable herein. For exdride;1,2-dichloropentyl succinic acid anhydride; hexenyl succinic acidanhydride; hexyl succinic acid; sulfurized 3-methylpentenyl succinicacid anhydride; 2,3-dimethylbutenyl succinic acid anhydride;3,3-dimethylbutenyl succinic acid; 1,2-dibromo-2-ethylbutyl succinicacid; heptenyl succinic acid anhydride; 1,2-diiodooctyl succinic acid;octenyl succinic acid anhydride; 2-methylheptenyl succinic acidanhydride; 4-ethylhexenyl succinic acid; 2-isopropylpentenyl succinicacid anhydride; noneyl succinic acid anhydride; 2- propylhexenylsuccinic acid anhydride; decenyl succinic acid; decenyl succinic acidanhydride; 5- methyl-2-isopropylhexenyl succinic acid anhydride;1,2-dibromo-2-ethy1octenyl succinic acid anhydride; decyl succinic acidanhydride; undecenyl succinic acid anhydride; 1,2-dichloroundecylsuccinic acid; 3-ethyl-2-t-butylpentenyl succinic acid anhydride;dodecenyl succinic acid anhydride; dodecenyl succinic acid;2-propylnonenyl succinic acid anhydride; 3-butyloctenyl succinic acidanhydride; tridecenyl succinic acid anhydride; tetradecenyl succinicacid anhydride; hexadecenyl succinic acid anhydride; sulfurizedoctadecenyl succinic acid; octadecyl succinic acid anhydride;1,2-dibromo 2 methylpentadecenyl succinic acid anhydride;8-propylpentadecyl succinic acid anhydride; eicosenyl succinic acidanhydride; 1,2 dichloro 2 methylnonadecenyl succinic acid anhydride;2-octyldodecenyl succinic acid; 1,2-diiodotetracosenyl succinic acidanhydride; hexacosenyl succinic acid; hexacosenyl succinic acidanhydride; and hentriacontenyl succinic acid anhydride.

The methods of preparing the alkenyl succinic acid anhydrides are wellknown to those familiar with the art. The most feasible method is by thereaction of an olefin with maleic acid anhydride. Since relatively pureolefins are difficult to obtain, and when thus obtainable, are often tooexpensive for commercial use, alkenyl succinic acid anhydrides areusually prepared as mixtures by reacting mixtures of olefins with maleicacid anhydride. Such mixtures, as well as relatively pure anhydrides,are utilizable herein.

In general, the alkenyl succinic acid anhydride reactant is reacted withthe intermediate prodduct in a proportion of between about (.'r.1) andabout one mole of alkenyl succinic acid anhydride reactant for each moleof polyalkylenepolyamine reactant used in the preparation of theintermediate product, :1: representing the number of nitrogen atoms inthe polyalkylenepolyamine reactant molecule. The sum of the number ofmoles of monocarboxylic acid reactant and of alkenyl succinic acidanhydride reactant reacted with each mole of polyalkylenepolyaminereactant, in accordance with this invention, must not exceed the numberof nitrogen atoms in the polyalkylenepolyamine reactant molecule.Accordingly, the maximum number of moles of alkenyl succinic acidanhydride reactant used is the difference between the number of nitrogenatoms in the polyalkylenepolyamine reactant molecule and the number ofmoles of monocarboxylic acid reactant used per mole ofpolyalkylenepolyamine reactant. As mentioned hereinbefore, however, thefirst molecule of the monocarboxylic acid reactant appears to react withtwo nitrogen atoms. Accordingly, in order to achieve a reaction productwhich does notinvolve a physical mixture of the intermediate productand/or the reaction product, representing the complete chemicalinteraction of the reactants, with the alkenyl succinic acid anhydridereactant, the sum of the number of moles of the monocarboxylic acidreactant and of the alkenyl succinic acid anhydride reactant reactedwith each mole of polyalkylenepolyamine reactant must not exceed oneless than the number of nitrogen atoms in the polyalkylenepolyaminemolecule. In order words, the proportion of alkenyl succinic acidanhydride reactant to polyalkylenepolyamine reactant will vary between(x-2) :1, respectively and 1:1, respectively. For example, when twomoles of decanoic acid are reacted with one mole oftetraethylenepentamine to produce an intermediate product, one or twomoles, but not more than two moles, of an alkenyl succinic acidanhydride is reacted with this intermediate product to produce areaction product representing the complete chemical interaction of thereactants. However, three moles of an alkenyl succinic acid anhydridereactant can be reacted with this intermediate product to produce aproduct which comprises a physical mixture. Such a product iscontemplated herein.

The reaction between the alkenyl succinic acid anhydride reactant andthe intermediate product takes place at any temperature ranging fromambient temperatures and upwards. This reaction is apparently an amideformation reaction efiected by the well known addition of the anhydridegroup to an amino or imino group. This addition proceeds at anytemperature, but temperatures of about 100 C. or lower are preferred.When an alkenyl succinic acid is used, water is formed. Therefore, inthis case, the reaction temperature preferably should be higher thanabout 100 C.

The reaction between the alkenyl succinic acid anhydride reactant andthe intermediate roduct proceeds smoothly in the absence of solvents, atatmospheric pressure. However, the occurrence of undesirable sidereactions is minimized when a solvent is employed. Use of a solvent ispreferable when the reaction product is to be used in a steam turbinelubricating oil. .Since a small amount of water is usually formed alsowhen an alkenyl succinic acid anhydride is used in the reaction, thesolvent employed is preferably one which will form an azeotropic mixturewith water. These solvents have been discussed fully, hereinbefore, inconjunction with the reaction between the monocarboxylic acid reactantand the polyalkylenepolyamine reactant. The same solvents and the samemethods of using them ar applicable to the reaction between theinterperatures below 100 C. for a reaction time of less than one hour.In order to ensure complete reaction, however, it is preferred tocontinue heating for several hours. For example, when benzene is used asthe solvent at a temperature of 100-110" C., heating is continued forabout flve hours. When water is formed during the reaction, as when analkenyl succinic acid is used, the completion of the reaction isindicated by a substantial decrease in the formation of water. Ingeneral, the reaction time will vary between several minutes and aboutten hours.

Certain reaction products of this invention will be very viscous, oreven solid, rendering handling very difficult from a commercialstandpoint. Likewise, otherwise satisfactory antirust agents of thisinvention may be undesirably emulsive. These difficulties can often bealleviated by producing the reaction products in a mineral oil solutionor dispersion. The mineral oil can be added to the reaction mixture ofthe intermediate product and alkenyl succinic acid anhydride reactant,before they are reacted with each other. In an alternate procedure, thereaction product can be produced by the methods mentioned hereinbefore,and then the mineral oil can be added to the reaction product while itis still hot. If a solvent is used, it is immaterial whether the solventis removed before or after the addition of the mineral oil. Dependent onthe type of reaction product involved and of final product desired, themineral oil can be used in any amount, thereby producing reactionproducts containing from about one per cent by weight of oil up to asmuch as 99 per cent by weight of oil.

Without any intent of limiting the scope of the present invention, it ispostulated that the reaction products, representing the completechemical interaction of the reactants, contemplated herein, arecondensation products of the polyalkylenepolyamine reactant having atleast one free carboxylic acid group. For example, when one mole ofacetic acid is reacted with one mole of triethylenetetramine to producean intermediate product which is reacted with two moles of hexenylsuccinic acid anhydride, it is postulated that at least the followingthree reaction products and isomers thereof are possible. Theoreticallyall three could be present in varying amounts.

mediate product and the alkenyl succinic acid anhydride reactant. Forexample, satisfactory CH; (I311, products of this invention have beenprepared at C H C H H H temperatures varying between about 100 C. andabout 110 C., using an aromatic hydrocarbon COOH 00H solvent of thebenzene series. 0

The time of reaction is dependent on the size Nix-43H, tt-CH, of thecharge, the reaction temperature selected, N and the means employed forremoving any water C CAB from the reaction mixture. Ordinarily, theaddi- (H) tion of the anhydride reactant is substantially 0 completewithin a few minutes. The more emul- (H) 00H sive reaction products canbe produced at tem- OOH CH2CH2 (l H CH2CH2 N N-CH2CHzN-CH2 CHzNH-CCH1CHC-NHC Hr-CHzNCHz-CH,N I l I C =0 05H" =0 C JJH; ?Hz 5H) $11:

C(H)CQH|I 06H]! OOH OOH aceasve The reaction products probably containother substances. Accordingly, and in the interest of brevity, thereaction products are best defined by reciting the reactants and thenumber of moles of each which are used in the reaction. For example, thereaction product produced by reacting one mole of oleic acid with onemole of triethylene tetramine to produce an intermediate product whichis then reacted with two moles of decenyl succinic acid anhydride may bedefined as the reaction product of oleic acid (I) +triethylenetetramine(I) +decenyl succinic acid anhydride (II).

In addition to the products described in the illustrative examples, setforth hereinafter, nonlimiting examples of the reaction productscontemplated herein are those produced by reacting the followingcombinations of reactants: formic acid (IV)+tetra-(1-ethy1-2-benzylethylene) pentamine (I)+ethenyl succinic acidanhydride (1); acetic acid anhydride (I) +tri-(1-methyl-1-phenyl-3-propylpropylene)tetramine (I) +ethenyl succinic acid (II);acetyl fluoride (I) +triethylenetetramine (I) +hexeny1 succinic acidanhydride (II); fluoroacetic acid (II) +tetra-(1-methy1-3-benzylpropylene) pentamine (I)+ ethyl succinic acidanhydride (III); propionic acid (I) +penta (1 methyl-2-benzylethylene)-hexamine (I) +propenyl succinic acid anhydride (V); propiolic acid (I)+di-(1,18-dioctyloctadecylene) triamine (I) +sulfurized propenylsuccinic acid anhydride (1); fi-chloropropionic acid (II) +di(1,2-dimethyl-14-nonyltetradecylene) triamine (I) +butenyl succinic acid(I); bromoacetic acid (I) +dieicosylenetriamine (I) +2- methylbutenylsuccinic acid anhydride (H); isobutyric acid (III)+trioctadecylenetetramine (I)+1,2-dich1oropentyl succinic acid anhydride(I); a-bromobutyric acid (I) +tri-(1,15-dimethylpentadecy1ene)tetramine(I) +hexeny1 cinic acid (I) isocrotonic acid chloride (I) +penta (1methyli-nonylbutylene)hexamine (I) hexylsuccinic acid anhydride (IV);fi-ethylacrylic acid (II) +tetradecylenepentamine (I)+ sulfurized3-methylpentenyl succinic acid anhydride (II); valeric acid (I)+didodecylenetriamine (I) +2,3-dimethylbutenyl succinic acid anhydride(I); a-bromoisovaleric acid (III)+ tetra-(lA-dipropylbutylene) pentamine(I) 3,3- dimethylbutenyl succinic acid (I); allylacetic acid (II)+tridecylene-triamine (I)+1,2-dibromo-2-ethy1butyl succinic acid (I);hexanoyl bromide (I) +tri-(1,4-diethylbutylene) tetramine (I) +heptenylsuccinic acid anhydride (I); sorbic acid (IV) +tetraoctylenepentamine(I)+ 1,2-diiodoactyl succinic acid (I); fi-chloroacryli: acid (I)+penta- (1,2-dimethy1-l-isopropylethylene)hexamine (I) +octenyl succinicacid anhydride (V); nitrosobutyric acid (I) +di-(1- methyl4-ethylbutylene) triamine (I) +2-methylheptenyl succinic acid anhydride(II); aminovaleric acid (V) +penta-(1,5-dimethylamylene)- hexamine (I)+4-ethylhexenyl succinic acid (I); aminohexanoic acid (II)+tetra-(1,3-dimethylpropylene) pentamine (I) +2 isopropylpentenylsuccinic acid anhydride (III); heptanoic acid anhydride (I) +di (1methy1amylene)triamine (I) +noneyl succinic acid anhydride (II); 2-ethylhexanoic acid (III) +tri-(1,2,2-trimethylethylene) tetramine(I)+2-propyl-hexenyl succinic acid anhydride (I); a-bromooctanoic acid(I) +pentaamylene-hexamine (I) +decenyl .succinic acid anhydride (IV);decanoic acid (I)+ d1 (1 methylbutylene)triamine (I) +deceny1 succinicacid (I); dodecanoic acid (V) +hexa- SUC- 12 (1,1 dimethylethylene)heptamine (I) +5-methy1-2-isopropylhexenyl succinic acid anhydride (II);undecylenic acid (II) +tetrabutylenepentamine(I)+1,2-dibromo-2-ethylocteny1 succinic acid anhydride (II);tetradecanoic acid (111)4- penta (l-methyl-propylene) hexamine (I) +00-tenly succinic acid anhydride (II); hexadecanoic acid(I)+tri(ethylethylene)tetramine (I)+ decyl succinic acid anhydride(III); palmitic acid (VI) +hexapropyleneheptamine (I) +undecenylsuccinic acid anhydride (I); oleic acid (I) +di (methylethylene)triamine(I)+1,2 -dichloroundecyl succinic acid (I); heptadecanoic acid (IV)+tetraethylenepentamine (I) +3-ethyl-2-t-butylpentenyl succinic acidanhydride (1); stearic acid (I)+hexapropyleneheptamine (I)+ dodecenylsuccinic acid anhydride (VI); linoleic acid (IV) +hexa (1,1dimethylethylene) heptamine (I) +dodecenyl succinic acid (I); linoleicacid (I) +triethylene-tetramine (I) +2-propylnoneyl succinic acidanhydride (I11); phenylstearic acid (I) +diethylenetriamine (I) +3-butyloctenyl succinic acid anhydride (I); xylylstearic acid (II)+di-(methylethylene) triamine (I) +tridecenyl succinic acid anhydride(I); a-dodocyltetradecanoic acid (I) +diethylenetriamine (I)+tetradecenyl succinic acid anhydride (I); arachidic acid(II)+tetra-(1,3-dimethylpropylene) pentamine (I) +hexadeceny1 succinicacid anhydride (III); behenic acid (I) +tetrabutylenepentamine (I)+su1furized octadenecyl succinic acid anhydride (II); behinolic acid(III) +tetraethylene pentamine (I) +octadecy1 succinic acid anhydride(II); erucic acid anhydride (I) +hexaethyleneheptamine (I)+1,2-dibromo-2-methylpentadecenyl succinic acid anhydride (V); melissic acid(I) +diethylenetri amine (I) +8-propylpentadecyl succinic acid anhydride(I); hexahydrobenzoic acid (II)+triethylenetetramine (I) +eicosenylsuccinic acid anhydride (II); hexahydrobenzoyl chloride (I)dipropylenetriamine (I) +decenyl succinic acid anhydride (1); furoicacid (I) +di-(1-methylbutylene) triamine (I) +1,2 dichloro2-methylnonadecyl succinic acid anhydride (II); chlorofuroic acid (V)+penta-(l-methylpropylene) hexamine (I) +2-octyldodecenyl succinic acid(I); thiophenecarboxylic acid (I) +diethylenetriamine(I)+1,2-diiodotetracosenyl succinic acid anhydride (I); picolinic acid(III) +pentaamylenehexamine (I) +hexacoseny1 succinic acid (II);nicotinic acid (I) +tetraethylenepentamine (I) +hexacoseny1 succinicacid anhydride (IV); benzoic acid (HI) +tetraoctylenepentamine (I)+hentriacontenyl succinic acid anhydride (II); benzoyl iodide (I)+triethylenetetra- .nine (I) +octenyl succinic acid anhydride (H);toluic acid anhydride (I) +diethylene-triamine (I) +hentriacontenylsuccinic acid (I); xylic acid (II)+penta-(1,2-dimethyl-1-isopropylethylene) hexamine (I) +hexadecenylsuccinic acid anhydride (IV); chloroanthranilic acid (I)+tetraethylenepentamine (I) +8 propylpentadecenyl succinic acidanhydride (III); chloronitrobenzoic acid (I) +diethylenetriamine(I)+decenyl succinic acid anhydride (II); cinnamic acid (IV)+hexapropy1eneheptamine (I) hentriacontenyl succinic acid anhydride(II); aminocinnamic acid (II) +triethylenetetramine (I) +hexenylsuccinic acid anhydride (II); salicylic acid (II) +triethylenetetramine(I) +tetradecenyl succinic acid anhydride (II); hydroxytoluic acid (I)+tri-(1,2,2,-trimethylethylene)- tetramine (I) +heptenyl succinic acidanhydride (HI); iodosalicylic acid (II)+hexapropyiene- 13 heptamine (I)+octenyl succinic acid anhydride (V); and naphthoic acid (I)+tetraethylenepentamine (I)+hexacosenyl succinic acid anhydride (IV).

The following specific examples are for the purpose of illustrating thepresent invention, and of demonstrating the advantages thereof. It mustbe strictly understood that this invention is not to be limited to theparticular reactants and molar proportions employed, or to theoperations and manipulations described therein. A wide variety of otherreactants and molar proportions, as set forth hereinbefore, can be used.as those skilled in the art will readily understand.

The alkenyl succinic acid anhydrides used in the following specificexamples, except in Example 75, are commercial mixtures of alkenylsuccinic acid anhydrides in which the number of carbon atoms in the al'enyl radical varies between specified limits. The Cs-sASAA is a mixtureof hexenyl, heptenyl, and octenyl succinic acid anhydrides; Ca 1oA.SAAis a mixture of octenyl nonenyl, and decenyl succinic acid anhydrides;and C1o-12ASAA is a mixture of decenyl, undecenyl, and dodecenylsuccinic acid anhydrides. These products are predominantly mixtures ofrelative pure anhydrides. Sometimes, however, they contain minor amountsof the corresponding alkenyl succinic acids, but these are utilizable asset forth hereinbefore.

EXAMPLE 2 Oleic acid (I) +trz'ethylenetetramine (I) C1o-12ASAA (II) Onemole (282 grams) of oleic acid and one mole 146 grams) oftriethylenetetramine were placed in a reaction vessel provided with amechanical stirrer, a thermometer, and a reflux takeoff, i. e., acondenser device adapted to remove water from an azeotropic mixturethereof, as it is evolved from the reaction mixture. The reflux takeoffwas filled with benzene, and the stirred reactants were heated to about100 C. Benzene was added to the reaction mixture until refluxingoccurred with the reactants at about 145 C. The reaction was continuedat this temperature for about 8 hours, during which period of time 33milliliters of an aqueous layer (primarily water) were collected. Thesolvent (benzene) was removed from the reaction mixture at a pottemperature of 145 C. under reduced pressure. This intermediate producthad an N. N. (neutralization number=number of mg. KOH equivalent to onegram of product) of 4.0.

Forty-one grams of this intermediate product and 0.2 moles (58.8 grams)of C1o-I2ASAA were placed in a reaction vessel provided with amechanical stirrer, thermometer, and reflux takeoff. Upon stirring, thereaction mixture became viscous, and some heat was evolved. Benzene wasadded to the reaction mixture, and heat was applied so that refluxingoccurred with the reactants at about 105 C. After five hours, thebenzene was removed by distillation at a pot temperature of 105 C. underreduced pressure Th resultant reaction product had an N. N. of 55.2.Pertinent data for the product are set forth in Table I.

EXAMPLE 3 grams) were placed in a reaction vessel provided with amechanical stirrer, a thermometer. and a reflux takeoff in which adrying tube filled with anhydrous calcium chloride was-fitted to the topof the condenser. The reactants were heated to C., and benzene was addedto the system until refluxing occurred at a pot temperature of 140-145C. After 10 hours of reaction, 33 milliliters of water had beencollected. Benzene was removed under reduced pressure at a pottemperature of C. The resultant intermediate product had an N. N. of12.9.

Thirty-six grams of this intermediate product and 29.4 grams (0.1 mole)of C1o-12ASAA were heated to 140 C. in a reaction vessel equipped with amechanical stirrer, a thermometer, and a reflux takeoff. Benzene wasadded and the rate of heating was adjusted to permit refluxing at a pottemperature of 140-145" C. for 8 /2 hours. Then the benzene was removedat a pot temperature of 140-145 C. under reduced pressure, leaving areaction product having an N. N. of 61.3. Pertinent data for thisproduct are set forth in Table V.

EXAMPLE4 Oleic acid (II)+tetraeth1/lenepentamine (I)+ C8-10ASAA (II)Thirty-six grams of the intermediate product of Example 3 and 25.8 grams(0.1 mole) of CZ'l0ASAA were heated in a reaction vessel equipped asdescribed hereinbefore under a benzene reflux at a pot temperature of140-150" C. for 8 hours. Some water (0.3 milliliter) was collected.Benzene was removed under reduced pressure at a pot temperature of140-150 C. The resultant product had an N. N. of 48.7. Pertinent datafor this product are set forth in Table V.

EXAMPLE 5 Oleic acid (II)+tetraethylenepentamine (I)+ C6BASAA (II)Thirty-six grams of the intermediate product of Example 3 and 22.3 grams(0.1 mole) of Cs-aASAA were heated to 144 C. in a reaction vesselprovided with a mechanical stirrer, a thermometer, and a reflux takeoff.Benzene was added, and refluxing was maintained for 8 hours with thereactants at 140-150 C. Water (0.3 milliliter was collected. Benzene wasremoved under reduced pressure at a pot temperature of 140-150 C. Theresultant product had an N. N. of 58.4. Pertinent data for thisproduct'areset forth in Table V.

EXAMPLE 6 Oleic acid (l-i-diethylenetriamine (1+ CID-12ASAA (I) Oleicacid (0.1 mole) (28.2 grams) and diethylenetriamine (0.1 mole) (10.3grams) were heated to 140 C. in a reaction vessel provided with amechanical stirrer, a thermometer, and a reflux takeoff. Benzene wasadded to the system so that refluxing took place at 140-145 C. Afternine hours of reaction, nine milliliters of an aqueous liquid werecollected and the reaction was considered complete. The benzene wasremoved by distillation under reduced pressure. The intermediate productthus produced had an N. N. of 5.4.

About 18.3 grams of this intermediate product and 0.05 mole (14.7 grams)of C1o-12ASAA were heated to 105 C. in a reaction vessel provided asdescribedhereinbefore. Benzene was added so that refluxing wasmaintained for five hours 15 at a pot temperature of 1051l0 C. Water(0.5 milliliter) was collected. The benzene was removed by vacuumdistillation at a pot temperature of l110 C. The resultant reactionproduce had an N. N. of 46.8. Pertinent data for this product are setforth in Table VIII.

EXAMPLE 7 Oleic acid (I) +triethylenetetramine (I) C1o-12ASAA (II) in a50-per cent oil solution A reaction product was produced in the samemanner as the product described in Example 2, with the exception that99.8 grams of mineral lubricating oil A (defined hereinafter) was addedto the intermediate product and the C1o-1zASAA prior to reacting them.The resultant homogeneous mineral oil solution contained about 50 percent by weight of the reaction product and it had an N. N. of 26.5.Pertinent data for this product are set forth in Table I.

EXAMPLES 8 THROUGH 19 Oleic acid (I) +triethyleuetetramiue (I) variousASAAS I-III) Oleic acid was reacted with triethylenetetramine, in amolar proportion of 1:1, as described in Example 2, to produce anintermediate product. Portions of this product were reacted withCc-BASAA, Ca1oASAA, or C1o-12ASAA in various molar proportions of ASAAto triethylenetetramine and under varied reaction conditions. Pertinentdata for these products are set forth in Table I.

EXAMPLES 20 THROUGH 27 Various acids (I) +triethyleuetetramiue (I)C1o-12ASAA (II) Each of a variety of monocarboxylic acids was reactedwith triethylenetetramine in a molar proportion of 1:1, as described inExamples 2 through 7. The resultant intermediate products were eachreacted with C1c-12ASAA, in a molar proportion of triethylenetetramineto ASAA of 1:2, respectively, as set forth in the data given in TableII.

EXAIMPLES 28 THROUGH 32 Various acids (II-III) +triethyleuetetramine (I)+C1o-12ASAA (I-II) Each of a variety of monocarboxylic acids was reactedwith triethylenetetramine, as described in Examples 2 through 7, invarious molar proportions. Portions of the resultant intermediateproducts were reacted with C1o-12ASAA in various molar proportions ofASAA to triethylenetetramine and under varied conditions, as defined inTable III.

EXAMPLES 33 THROUGH 42 Various acids (1) +tetraethyleuepentamine (I)C1o-12ASAA (I-IV) Each of a variety of acids was reacted withtetraethylenepentamine, as described in Examples 2 through 7, in a molarproportion of 1:1. The resultant intermediate products were reacted withC1o-12ASAA within a wide range of molar proportions of ASAA totetraethylenepentamine, in accordance with the data set forth in TableIV. EXAMPLES 43 THROUGH 57 Oleic acid (II) +tetraethylenepentamine (I)various ASAAS (I-III) An intermediate product was produced in accordancewith the procedure set forth in Ex- 16 ample 2, by reacting oleic acidwith tetraethylenepentamine, in a molar proportion of 2:1, respectively.Portions of this product were reacted with C6-sASAA, Ca-mASAA, 01C1o-12ASAA in various molar proportions of ASAA totetraethylenepentamine, as set forth in Table V.

EXAMPLES 58 THROUGH 63 Various acids (II) +tetraethylenepentamine (I)Cio-12ASAA (II-III) Each of a variety of monocarboxylic acids, and amixture of two of these acids, were reacted with tetraethylenepentaminein a molar proportion of 2:1, respectively in accordance with theprocedures described in Examples 2 through 7. Portions of the resultantintermediate products were reacted with C1o-12ASAA in molar proportionsof tetraethylenepentamine to ASAA varying between 1:2, respectively, and1:3, in accordance with the data set forthin Table VI.

EXAMPLES 64 THROUGH 68 Various acids (III-IV) +tetraethylenepeutamine(I) +C1c-12ASSA (I-II) Each of a variety of monocarboxylic acids. and amixture of two of these acids, were reacted with tetraethylenepentamine,in molar proportions varying between 3:1, respectively, and 4:1, by theprocedures described in Examples 2 through 7. The resultant intermediateproducts were reacted with 010-12ASAA in molar proportions oftetraethylenepentamine to ASSA varying between-about 1:1, respectively,and 1:2, as defined by the data given in Table VII.

EXAIVIPLES 69 THROUGH 74 Various acids (I-II) +diethylenetriamine (I)C1o-12ASSA (I-II) Each of a variety of monocarboxylic acids was reactedwith diethylenetriamine, by the procedures described in Examples 2through 7, in molar proportions of 1:1, respectively, to 2:1,respectively. Portions of the resultant intermediate products werereacted with C1'o-12ASAA. in molar proportions of diethylenetriamine toASAA varying between 1:1, respectively, and 1:2, respectively. Pertinentdata for these products are set forth in Table VIII.

EXAIVIPLE75 Oleic acid (I) +triethylenetetramine (I) +iriisobutenylsuccinic acid anhydride (II) in a 50- per cent oil solutionSingle-distilled oleic acid (red oil) (2 moles) (564 grams) andtriethylenetetramine (1.5 moles) (219 grams) were placed in a reactionvessel which was provided with a stirrer, a thermometer, and a refluxtakeofi trap. The refiux takeofi was filled with benzene and the stirredreactants were heated to C. Then, 30 milliliters of benzene were addedto the reaction mixture such that refluxing occurred with a pottemperature of 140-142 C. The reaction was continued for ten hours,during which time 57 milliliters of an aqueous layer (primarily water)was collected. The solvent was removed from the reaction mixture bydistillation at a pot temperature of C., and under about 20 millimeterspressure. This intermediate product had an N. N. of 5.5 and an averagemolecular weight of about 484.

About 0.466 moles (225.7 grams) of'this ir -rcatalyticallyed rusting ofbout 50 per cent, rust agent.

18 This product contained a per cent and 0.008 per cent of product in aleaded, gasoline completely inhibit n the ASTM rust test, using F. Thisis a. modification valuate antirust agents in Blends of 0.002 per centin the eel: permitted about 5 per cent face to rust. Pertinent test datain lubricating oils are set forth by weight, of the active anti Blendsof 0.004

this reaction the metal specimens i distilled water at 80 of this testused to e light products.

of the metal sur for this product in Table IX.

m same gasoline st TABLE I hydride (produced in ac- U. 3. Patent No.2,380,699), and

ral oil B (defined hereinafter) action vessel. The reaction 5 crackedmeter, a stirin turn, was cona trap, and a vacuum e reaction ves- Thereaction for three Pertinent data for the products: Olelc acid (I)+lriethulenetetrami1w (I)+uuriu8 ASAAS (I-III) intermediate product.

The reaction product had an N. N. of

1 condliltitlms for reaciigon of ASAA with 1 'Iriet y enetetram e. ITested without oxidation inhibitors.:

00 grams of mine 24 l 2 .24 n m u m m B Cwmfi mll n w w 67 M77 U l l a mm I m M C N m m B B. m m mt id .x m mmmm ram 3%.... m xm m am umna mm mmm n "mm m .3 C E .1 c m pm 0 m M m T Dw T Dw I y d .r 00 an 0 m W m m mm m m m mm. mm m u u m m m Dw m Tun w u R t l r WWW wmWNOOOOOOOOOMMOOOMUOOIE MMM M 0000 m MW Mm mm OWOOW R m m M W 0 u M M w AH AAAAA w AAAAAAABBBAAAAAAAAAAA m w AAAAAAAA 0 s 1 m 0 %m%%%%mwm%%MMMMMJMM u W mm wmmmm m aodddcaddodddaaddd ao w m n 00000000 P00 00 0 00 cm .2. .32... m c e I 61060 .0 6336 53 4532 5 .1 n .m y 3 2 7 1410 m d1N ma an aw. name a mm M w mama mm m mm mac PUN m P N W r w a m rw aim:e III a 1 r e 1 v I: 1 v e Z S to Q0 mm \/e d S o U. n a M0000 m 3 an mmmama n m .M mm m Wm afi m R Bx IIIH N M m R .r m 0 i n i 8 535 m m". 5388 1355 5 .5 H H W m m m "W 3 O .i W 1H I TH T 1 E D n T E m i t a Wm%%M% B m MMWM 6 A m c n A s m n. mmmm m p 11 1111 11 11-V1 1 1 T M Mm mT d m W. w R m 8 m a R e a m R e.. m M d M T u G T 11 1 m M W 0 C t H 011111111 11111 11 1111 H1 nd 18 3 C G 8 221223.... I m f I 1. m 17 $22222 2222 2M2 W M V mW m 22222222 m M mmmMm 2m111 o 2 2 m o m nm a w Mn mM w a w P A w a A t H d m 6 junta". o ruin: u m m ammo mama w m m m. Munwnuwww m m M mm 000%. HH 0mm 0 m. m mm m S wmiwwiii m n. M CC CCCC CCCCCC C C W W A CCCCCCCC m M m I] 1 11 I. 0 11111 11 1111 11 1111 1 1 O 1E 03 111 1.41 r If 1 e I. flw mm 11 R111 LP. lhhl 1 1 o e M 11111111 Mm. 22232 1 .i 0.... i mm mm w m mfl S m Mh m P AA A imq m P A A a n M mm m m m e i e m A m m m m m m m mma P .m m m m n .m m T0 00 00 0 0 nduTTTT TT tmr m d dd dd d d mn m m EEEEEEEE m m m A T n h n n M u m om ATTTTTTTT m P n U h h u 0 0 mm a m T I u amm m u G nni" m w w I I n 0 m ma 6 mam ma m H u a n m mm a m mmmmmmma a a a a t a a ama a area m m u h5 0 n cflc ro 0 m m m m n wmfi DDOPOHPF hm m m 89 an 1 m m maaaaaam mmediate, 1.074 moles (285.7 grams) of triisobutenyl succinic acid ancordance with were placed in a-re' vessel was equipped with a thermorer, and an outlet tube which nected to a manometer,

pump. The reactants were heated, with stirring, to C. and the pressurein th sel was reduced to 50 millimeters.

was continued under these conditions hours.

TABLE VII Pertinent data for the produds: various acids(fll-m-Hetradhulenepentamim (I) +01o- ASAA (I-II) Rust Test Emulsion IMolar PMolar Reaction Conditions P d P MPei' gent'd Test, Break,

roporroporro er eta uste Min. Ex. fig Amine tion, ASAA tion, uct, Centon Acid to ASAA to N. N. Concn Amine Amine Temp., Time, Water ea ist.ist. 1%

C. Hrs. Remover Water Water Water NsCl Cc. Cc. 64 Olelc TEPA 3:1 010-12-1:1 145-150 6 Benzene- 35.8 0.05 A 36 40 65 do -do 3:1 Clll--- 2:1145-150 6 o 61.1 0.05 A 0 77 55 66 Dodecanoicu 0..... 3:1 010-12". 2:1140 8 0 55.8 i 20 0 27 5 67 l-Olelc-l-2- do"-.. 3:1 10l!--- 2:1 140 10do. 68.2 0.05 A 0 0 17 43 Dodecanc. as Oleic .--do----. 4:1 l0-lI--- 2:1105 5 do- 77.0 0.05 A 0 0 77 76 1 Conditions for reactions 0! ASAA withintermediate product. I Tetraethylenepentemine.

TABLE VIII Pertinent data for the products: various acids(II1')+diethulendriamim (I)+C1o-1:ASAA (I-II) Rust Test EmulsionIltioinr PMolar Reaction Conditiona P d P MPe;I(2ent d Testfimlxilreak,

roporroporro er eta uste Ex. fi a Amine tion, ASAA tion, uct, Cent OilAcid to ASAA to N. N Conan Amine Amine Temp., Time, Water Sea Dist.Dist. 1%

0. Hrs Remover Water Water Water NaOl Cc. Cc. 69 0le1c DETAZ 2:1 C o-u.1:1 105-110 5 Benzene. 80.5 0.05 A 72 75 70 0....... .do 1:1 Clo-1e.-.2:1 105 5 do 132.0 0.05 A 54 71 do 0..... 1:1 Clo-1a.-. Ltd 140 2-3Vacuum. 20.0 i 36 72 Oetadecanoic. .do.... 1:1 Clo-1s... 1.6:1 140 5Xylene. 30.1 8103 i 2 2 .1 73 .do do. 1:1 010-12- 2:1 140 6 do 56.8 0.05A 10 18 6 Oleic do. 1:1 Cit-1s... 1:1 105 5 Benzene. 46.8 0.05 A 70 6674 Dodecanoic o. 1:1 Clo-n..- 2:1 105 5 0..... 141.1 0.05 A 5 3 1Conditions for reaction 01 ASAA with intermediate product. 5Diethylenetrlamine.

8 Tested without oxidation inhibitors.

4 Dispersion in mineral oil.

TABLE IX Test data for product of Example 76 in oil In order todemonstrate the outstanding properties of the reaction products of thisinvention, typical rust test data and emulsion test data were obtainedfor mineral lubricating oil blends containing the reaction productsdescribed in the examples. Pertinent data are set forth in Tables Ithrough IX.

Mineral oil A used in these tests was a blend of solvent-refined,Mid-Continent residual stock with a. solvent-refined Mid-Continent(Rodessa) distillate stock. It had a specific gravity of 0.872, a flashpoint of 445 F., and a Saybolt Universal viscosity of 407.! seconds at100 F. Mineral oil B was a furfural-refined, Mid-Continent (Rodessa)distillate stock. It had a specific gravity of 0.860, a flash point of405 F., and a Saybolt Universal viscosity of 155 seconds at 100 F. Bothof these mineral lubricating oils are suitable for use in steamturbines. Unless otherwise indicated in the tables, the test oilcontained 0.2

per cent by weight of 2,6-di-t-butyl-4-methyl Rust Test Emulsiml phenoland 0.1 per cent by weight of phenyl- Per 5322. i fi' a-naphthylamine,both well-known antioxidants.

g Cent on The test method used to distinguish the rustsea Dist Dist 1PMmg charactenstws of lubricating 011 blends was Water Water Water theASTM test D665-44T for determining Rust Preventing Characteristics ofSteam Turbine 0 10 A 15 Oils in Presence of Water, in which synthetic01075 A 14 sea water was used as well as distilled water.

3-82 The synthetic sea water contained 25 grams of 0101 B .1 sodiumchloride, 11 grams of magnesium chlogfig i; ride hexahydrate, 4 grams ofsodium sulfate, and

0.003 B 1.2 grams of calcium chloride per liter. Ir. this 8:33? I g testa cylindrical polished steel specimen is suspended and soaked in 300cubic centimeters of the oil under test at 140 F. for thirty minutes.Thirty cubic centimeters of synthetic sea Water (or distilled water) areadded and the mixture is stirred at 1000 R. P. M. After 48 hours, thesteel specimen is removed and examined for evidence of rust on theportion of the specimen which hangs in the oil. In the tables, rust testresults are given in terms of per cent of exposed metal surface whichhas rusted. The complete rusting which is evident when uninhibited baseoils are tested is taken as per cent.

The emulsion test used is the emulsion test for lubricating oils,Federal Stock Catalog, section IV, part 5. Federal SpecificationsVV-L-791b, February 19, 1942. In test method 320.13, 40 cubiccentimeters of oil and 40 cubic centimeters of emulsant in a 100-cubiccentimeter cylinder are stirred with a paddle at 1500 R. P. M., for 5minutes, at 130 F. Separation of the emulsion is observed while thecylinder is kept at 130 F. The figures in the tables show the number ofminutes at which there is no continuous layer of emulsion between theoil and the emulsant, or the number of cubic .centimeters of emulsionpersisting at the end of thirty minutes.

From the data set forth in the tables, it will be apparent that goodvantirust characteristics are imparted to lubricating oils which containthe reaction products of the present invention. To be completelyacceptable for use in a turbine oil, an additive, preferably, should notimpart undesirable emulsion characteristics thereto. It will be apparentfrom the emulsion test data given in the tables that, as a class, thereaction products of this invention do not impart undesirable emulsioncharacteristics to the oil. Some products, however, do produce emulsiveoils. Several demulsifying agents are known, however, and incorporationof such agents in these emulsive oils improves the emulsion char-'acteristics thereof.

EXAIVIPLE '16 The rusting characteristics of a mineral lubricating oilcontaining the product of Example 11 (Table I) were further tested,along with the oxidation characteristics thereof, by means of the ASTMtest method D943-4'7T. In accordance with this test, the oil anddistilled water are placed in a large test tube, which is maintained at203 F. A polished copper-iron catalyst coil is inserted into the oil,but it does not extend into the water layer. Oxygen gas is passedthrough the water and oil at the rate of three liters per hourthroughout the 1000-hour test period. Test oil B contained by weight0.05 per cent of the product g Example 11, 0.2 per cent2,6-di-tbutyl-4-methyl-pheno1, and 0.1 per cent phenyle-naphthylaminewas not oxidized in this test as evidenced by an N. N. of 0.02. Thecatalyst coil showed no trace of rust. When the oil is tested withoutthe antirust additive the catalyst coil rusts within as short a periodof time as twentyfour hours.

EXAMPLE 77 Prevention of atmospheric corrosion In order to evaluate thenew reaction products as coating compounds for the prevention ofatmospheric corrosion, a test was run as follows: Two polished steelspecimens were coated with the product of Example 13 (Table I) bydipping them in a two per cent by weight solution of the product inbenzene. Likewise, two additional specimens were coated with the productof Example 3 (Table V). A fifth specimen was left uncoated, as thecontrol. These specimens were suspended in the chemical laboratory,exposed to the various vapors and fumes ordinarily found therein. After15 days of such exposure, none of the specimens showed visible signs ofcorrosion. Then each specimen was immersed in distilled water for about30 seconds, by raising a separate beaker of distilled water under eachone. The control specimen showed a light surface rusting about fiveminutes after this treatment. The coated specimens remained free ofcorrosion. After one hour, the immersion process was repeated. Sevendays thereafter, the coated specimens were still free of any trace ofcorrosion. The control specimen, on the other hand, was severelycorroded.

In the foregoing specific illustrative examples,

the effectiveness of the reaction products for the prevention of rust inlubricated systems and for the prevention of atmospheric corrosion hasbeen demonstrated. In addition to the use in turbine oils or as coatingagents, these reaction products are utilizable for numerous purposes.They can be added to a wide variety of vehicles to produce improvedcompositions. They can be dissolved in the vehicle, or they can bedispersed therein, in the form of suspensions or emulsions.

The vehicles can be liquids or plastics, the basic requirement beingthat they must be spreadable over metal surfaces. Spreading may beaccomplished by immersion, flooding, spraying, brushing, trowelling,etc. Additionally, the vehicle should be substantially neutral. It canbe oleaginous, i. e., substantially insoluble in water, or it can beaqueous. Aqueous vehicles include aqueous solutions of liquid, such asalcohol-water mixtures and the like. Oleaginous vehicles can behydrocarbon materials, such as mineral oils and hydrocarbon solvents, ornon-hydrocarbon materials, such as fatty oils and fats.

Non-limiting examples of suitable vehicles for the additives of thisinvention are mineral lubricating oils of all grades; gasolines andother li ht petroleum products, such as fuel oil; water; alcohols, suchas ethanol, isopropanol, butanol, cyclohexanol, methylcyclohexanol,octanol, decanol, dodecanol, hexadecanol, octadecanol, oleyl alcohol,benzyl alcohol, etc.; phenols; glycols, such as ethylene glycol,propylene glycol, butylene glycol, glycerol, etc.; ketones, such asacetone, methyl ethyl ketone, dipropyl ketone, cyclohexanone, etc.; ketoalcohols, such as acetol; ethers, such as d'ethyl ether, dipropyl ether,diethylene dioxide, dichloro diethyl ether, diphenyl oxide, diethyleneglycol, triethylene glycol, ethylene glycol monobutyl ether, etc.;natural esters, such as ethyl acetate, butyl propionate, cresyl acetate,dodecyl acetate, ethyl maleate, butyl stearate, tridecyl phosphate,tributyl trithiophosphate, triamyl phosphite, etc.; petroleum waxes,such as slack wax and parafiin wax; natural waxes, such as carnauba wax,japan wax, beeswax, etc.; natural fats and oils, such as sperm oil,tallow, cottonseed oil, castor oil, linseed oil, tung oil, soy bean oil,oiticica oil, tar oil, oleo oil, etc.; hydrocarbons and halogenatedhydrocarbons, such as butanes, chlorinated hexanes, octanes, brominateddecanes, dodecanes, Freon, eicosane, benzene, toluene, xylene, cumene,indene, alkyl naphthalenes, etc; greases; asphalts; chlorinatedpetroleum fractions, such as chlorowax; and paints, varnishes and thelike.

As those skilled in the art will readily appreciate, the applications ofthe compositions of the present invention are many. Lubricating oils ofall types usually permit corrosion of metal surfaces. This poses aproblem in the lubrication of all types of engines, particularly steamturbines. Lubricating oils containing the reaction products of thisinvention are effectively inhibited against such corrosion. Diesel fuelscontaining these additives will have less tendency to corrode injectionnozzles. Steam cylinder oils and cutting oils can be inhibited againstcorrosive tendencies by the addition thereto of these new additives,particularly the more emulsive types. Greases can be inhibited likewise.Additionally, the more emulsive products of this invention can besubstituted in whole or in part for the emulsifying agents commonly usedin compounding greases, cutting oils, steam cylinder oils, etc.Hydraulic systems can be protected against corrosion by using hydraulicfluids containing the additives of the present invention.

The storage of infrequently used machinery, and the shipment and storageof metal shapes and metal parts, such as machined sewing machine partsor gun parts, present corrosion problems. Such corrosion can beprevented by treating them with slushing oils containing the additivesof this invention, by coating them with organic solvent solutions ordispersions of these additives, such as the benzene solutions describedhereinbefore, or by treating the surfaces thereof with dispersions ofthese additives in water. Corrosive tendencies of coolants andantifreeze solutions or mixtures, such as those used as coolants ininternal combustion engines, can be reduced by addition thereto of thereaction products of this invention. Such antifreezes include water,alcohol-water, glycols, glycol-water, etc. When gasoline and other fuelsare stored in drums or tanks, water often enters the storage space, asby breathing, and corrodes the inner surfaces thereof. This can beprevented through the use of the additives contemplated herein.

Relatively more permanent corrosion-preventive coatings can be producedby the application to metal surfaces of paints, and the like, containingthe additives of this invention. Vehicles utilizable for this purposeare paints, varnishes, lacquers, drying oils, asphalt roofingcompositions, and the like.

The amount of the reaction products which are added to a vehicle toproduce a composition in accordance with this invention varies betweenabout 0.001 per cent and about 50 per cent by weight, depending on thespecific use contemplated and on the specific reaction productsselected. Generally, it is sufficient to use an amount varying between0.01 per cent and about per cent. However, smaller amounts, as low asabout 0.001 per cent, will be effective in some cases. Likewise, amountsup to as much as about 50 per cent are required when the vehiclecontains resinous bodies, or when the reaction product is also used asan emulsifier, such as in a steam cylinder oil.

Other substances in addition to the reaction products of this inventioncan be added to the compositions contemplated herein to impart otherdesirable properties thereto. For example, there may be addedantioxidants, pour point depressants, V. I. improvers, antidetonants,cetane number improvers, emulsifiers, thinners, driers, etc.

Further examples of the preparation of the intermediate products of thisinvention and of their utility other than as intermediates for producingthe antirust agents of this invention are set forth in two copendingapplications of the present inventors. One application, Serial Number115,948, filed September 15, 1949, relates to an emulsifiable oilcomprising an oil and a small amount of the reaction product of apolyalkylenepolyamine with a monocarboxylic acid containing betweenabout fourteen carbon atoms and about thirty carbon atoms per molecule.The application, Serial Number 122,353, filed October 19, 1949, isconcerned with gasolines containing the reaction product of apolyalkylenepolyamine with an aliphatic monocarboxylic acid havingbetween about eight and about thirty carbon atoms per molecule. Thereaction produce, per se, is claimed in the latter application.

Although the present invention has been described with preferredembodiments, it is to be understood that-modifications may be resortedto without departing from the spirit and scope thereof, as those skilledin the art will readily understand. Such variations and modificationsare considered to be within the purview and scope of the appendedclaims.

We claim:

1. A corrosion-inhibiting composition which comprises -a substantiallyneutral vehicle containing between about 0.001 per cent and about 50 percent by weight of the reaction product obtained by reacting amonocarboxylic acid with a polyalkylenepolyamine having one morenitrogen atom per molecule than there are alkylene groups in themolecule, in a molar proportion varying between about one and about(::-I) to one, respectively, wherein :1: represents the number ofnitrogen atoms in the polyalkylenepolyamine molecule, to produce anintermediate product, and reacting an alkenyl succinic acid anhydridewith said intermediate product, in a molar proportion varying betweenabout 2-1) and about one to one, respectively; the sum of the number ofmoles of said monocarboxylic acid and of said alkenyl succinic acidanhydride reacted with each mole of said polyalkylenepolyamine being nogreater than 2..

2. The composition of claim 1, wherein said monocarboxylic acid is analiphatic monocarboxylic acid.

3. The composition of claim 2, wherein said polyalkylenepolyamine is apolyethylenepolyamine having between two and six ethylene groups permolecule.

4. The composition ofv claim 1, wherein said vehicle is an oleaginousvehicle.

5. The composition of claim 1, wherein said vehicle is an aqueousvehicle.

6. The composition of claim 1, wherein said vehicle is a hydrocarbonvehicle.

'7. The composition of claim 1, wherein said vehicle is a minerallubricating oil.

8. The composition of claim 1, wherein said vehicle is a non-hydrocarbonvehicle.

9. The composition of claim 1, wherein said vehicle is a fatty oil.

10. The reaction product obtained by reacting a monocarboxylic acid witha polyalkylenepolyamine having one more nitrogen atom per molecule thanthere are alkylene groups in the molecule, in a molar proportion varyingbetween about one and about (ac-1) to one, respectively, wherein :1:represents the number of nitrogen atoms in the polyalkylenepolyaminemolecule, to

molecule, in a molar proportion varying betweenabout one and about(:c-2) to one, respectively, wherein :1: represents the number ofnitrogen atoms in the polyalkylenepolyamine molecule, to produce anintermediate product, and reacting an alkenyl succinic acid anhydridewith said intermediate product, in a molar proportion varying betweenabout (3-2) and about one to one,

. 27 respectively; the sum of the number of moles of said monocarboxylicacid and of said alkenyl succinic acid anhydride reacted with each moleof said polyalkylenepolyamine being no greater than (:c-l).

12. The reaction product obtained by reacting an aliphaticmonocarboxylic acid with a polyethylenepolyamine having one morenitrogen atom per molecule than there are ethylene groups in themolecule and having between about two and about six ethylene groups permolecule, in a molar proportion varying between about one and about(ac-1) to one, respectively, wherein :n represents the number ofnitrogen atoms in the polyethylenepolyamine molecule, to produce anintermediate'product, and reacting an alkenyl succinic acid anhydride,having between about 8 and about 18 carbon atoms per alkenyl radical,

with said intermediate product, in a molar proportion varying betweenabout (:1:1) and about one to one, respectively; the sum of the numberof moles of said aliphatic monocarboxylic acid and of said alkenylsuccinic acid anhydride reand about six ethylene groups per molecule, in

a molar proportion varying between about one and about (18-2) to one,respectively, wherein :1: represents the number of nitrogen atoms in thepolyethylenepolyamine molecule, to produce an intermediate product, andreacting an alkenyl succinic acid anhydride, having between about 8 andabout 18 carbon atoms per alkenyl radical, with said intermediateproduct, in a molar proportion varying between about (cc-2) and aboutone to one, respectively; the sum of the number of moles of saidaliphatic monocarboxylic acid and of said alkenyl succinic acidanhydride reacted with each mole of said polyethylenepolyamine being nogreater than (11-1).

14. The reaction product obtained by reacting an aliphaticmonocarboxylic acid with a polyethylenepolyamine having one morenitrogen atom per molecule than there are ethylene groups in themolecule and having between about two and about six ethylene groups permolecule, in a molar proportion varying between about one and about (x1)to one, respectively, wherein a: represents the number of nitrogen atomsin the polyethylenepolyamine molecule, to produce an intermediateproduct, and reacting an alkenyl succinic acid anhydride having betweenabout ten carbon atoms and about twelve'carbon atoms per alkenyl radicalwith said intermediate product, in a molar proportion varying betweenabout (x-l) and about one to one, respectively; the sum of the number ofmoles of said aliphatic monocarboxylic acid and of said alkenyl succinicacid anhydride reacted with each mole of said polyethylenepolyaminebeing no greater than :11.

15. The reaction product obtained by reacting oleic acid withtriethylenetetraminain a molar 28 acted with each mole of saidtriethylenetetramine being no greater than four. '16. The reactionproduct obtained by reacting oleic acid with triethylenetetramine, in amolar proportion of aboutone to one, respectively, to produce anintermediate product, and reacting triisobutenyl succinic acid anhydridewith said intermediate product, in a molar proportion of about two toone, respectively.

1'7. The reaction product obtained by reacting dodecanoic acid withtetraethylenepentamine, in

per alkenyl radical with said'intermediate prod-' uct, in a molarproportion varying between about four and about one to one respectively;the sum of the number of moles of said dodecanoic acid and of saidalkenyl succinic acid anhydride reacted with each mole of saidtetraethylenepentamine being no greater than five.

18. The reaction product obtained by reacting dodecanoic acid withtetraethylenepentamine, in a molar proportion of about two to one,respectivel y, to produce an intermediate product, and reacting analkenyl succinic acid anhydride having between about ten carbon atomsand about twelve carbon atoms per alkenyl radical with said intermediateproduct, in a molar proportion of about three to one, respectively.

19. The reaction product obtained by reacting oleic acid withtriethylenetetramine, in a molar proportion varying between about oneand about three to one; respectively, to produce an interproportionvarying between about one and about three to one, respectively, toproduce an intermediate product, and reacting triisobutenyl succinicacid anhydride with said intermediate product, in a molar proportionvarying between about three and about one to one, respectively; the sumin a molar proportion varying between about three and about one to one,respectively; the sum of the number of moles of said oleic acid and ofsaid alkenyl succinic acid anhydride reacted with each mole of saidtriethylenetetramine being no greater than four.

20. The reaction productobtained by reacting oleic acid withtriethylenetetramine, in a molar proportion of about three to one,respectively, to produce an intermediate product, and reacting analkenyl succinic acid anhydride having between about ten carbon atomsand about twelve carbon atoms per alkenyl radical with said intermediateproduct, in a molar proportion of about one to one, respectively.

21. A mineral oil'containing between about 0.01 per cent and about 10per cent by weight of the reaction product obtained by reacting oleicacid with triethylenetetramine, in a molar proportion of about one toone, respectively, to produce an intermediate product, and reactingtriisobutenyl succinic acid anhydride with said intermediate product, ina molar proportion of about two to one, respectively.

22. A mineral oil containing between about 0.01, per cent and about 10per cent by weight of the reaction product obtained by reactingdodecanoic acid with tetraethylenepentamine, in a molar proportion ofabout two to one, respectively, to produce an intermediate product, andreacting an alkenyl succinic acid anhydride having between about 10carbon atoms and about 12 carbon atoms per alkenyl radical with saidintermediate product, in a molar proportion of about three to one,respectively.

reaction product obtained by reacting oleic acid withtriethylenetetramine, in a. molar proportion of about three to one,respectively, to produce 5 in a molar proportion of about one to one,re- 10 spectively.

RALPH V. WHITE. HENRY D. NORRIS. PHIILIP S. LANDIS.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,194,419 Chwala. Mar. 19, 19402,355,837 Wilson Aug. 15, 1944 2,374,354 Kaplan Apr. 24, 1945 2,473,577De Groote et a1. June 21, 1949 2,475,409 Smith et a1. July 5, 19492,490,744 Trigg et a1 Dec. 6, 1949 2,540,800 Trigg Feb. 6, 1951

1. A CORROSION-INHIBITING COMPOSITION WHICH COMPRISES A SUBSTANTIALLYNEUTRAL VEHICLE CONTAINING BETWEEN ABOUT 0.001 PER CENT AND ABOUT 50 PERCENT BY WEIGHT OF THE REACTION PRODUCT OBTAINED BY REACTINGMONOCARBOXYLIC ACID WITH A POLYALKYLENEPOLYAMINE HAVING ONE MORENITROGEN ATOM PER MOLECULE THAN THERE ARE ALKYLENE GROUPS IN THEMOLECULE, IN A MOLAR PROPORTION VARYING BETWEEN ABOUT ONE AND ABOUT(X-1) TO ONE, RESPECTIVELY, WHEREIN X REPRESENTS THE NUMBER OF NITROGENATOMS IN THE POLYALKYLENEPOLYAMINE MOLECULE, TO PRODUCE AN INTERMEDIATEHYDRIDE WITH SAID INTERMEDIATE SUCCINIC ACID ANHYDRIDE WITH SAIDINTERMEDIATE PRODUCT, IN A MOLAR PROPORTION VARYING BETWEEN ABOUT (X-1)AND ABOUT ONE TO ONE, RESPECTIVELY; THE SUM OF THE NUMBER OF MOLES OFSAID MONOCARBOXYLIC ACID AND OF SAID ALKENYL SUCCINIC ACID ANHYDRIDEREACTED WITH EACH MOLE OF SAID POLYALKYLENEPOLYAMINE BEING NO GREATERTHAN X.